DFT study of Raman spectra of...

The FT-Raman spectrum of the hexakis(4-N'(-di(4-oxyphenethylamino)-(thio)phosphonyl)-N'-methyl-diazobenzene)cyclotriphosphazene which is the first generation dendrimer G1 built from the cyclotriphosphazene core, six arms -O-C6H4-CH=N-N(CH3)-P(S)< and twelve 4-oxyphenethylamino terminal groups -O-C6H4-(CH2)2-NH2 G1 has been recorded. The structural optimization and normal mode analysis were performed for model compound C, consisting of cyclotriphosphazene core, one arm -O-C6H4-CH=N-N(CH3)-P(S)< and two 4-oxyphenethylamino terminal groups -O-C6H4-(CH2)2-NH2 on the basis of the density functional theory (DFT) at the PBE/TZ2P level. The calculated geometrical parameters and harmonic vibrational frequencies are predicted in good agreement with the experimental data. It was found that G1 has a concave lens structure with planar -O-C6H4-CH=N-N(CH3)-P(S)< fragments and slightly non-planar cyclotriphosphazene core. The 4-oxyphenethylamino groups attached to different arms show significant deviations from a symmetrical arrangement relative to the local planes of repeating units. The experimental Raman spectra of G1 dendron was interpreted by means of potential energy distribution. Relying on DFT calculations, as well as on experimental information, a spectral interpretation was proposed.